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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Chemical stability enhancement of lithium conducting solid electrolyte plates using sputtered LiPON thin film

Sputter deposition of LiPON films directly onto high Li+ conductivity solid electrolyte plates has been investigated as a means to minimize the reactivity of the plates to metallic Li. The LiPON films were shown to effectively passivate the plates in contact with metallic Li, in contrast to unpassivated plates that reacted immediately in contact with Li metal.

LiPON lithium metals electrolyte plates↗
DOE OSTI2021

Electrolysis on a Chip with Tunable Thin Film Nanostructured PGM Electrocatalysts Generated from Self-Assembled Block Copolymer Templates

Self-assembled block copolymers are promising templates for fabricating thin film materials with tuned periodic feature sizes and geometry at the nanoscale. Here, a series of nanostructured platinum and iridium oxide electrocatalysts templated from poly(styrene)-block-poly(vinyl pyridine) (PSbPVP) block copolymers via an incipient wetness impregnation (IWI) pathway is reported. Both nanowire and nanocylinder electrocatalysts of varying feature sizes are assessed and higher catalyst loadings are achieved by the alkylation of the pyridine moieties in the PVP block prior to IWI. Electrocatalyst evaluations featuring hydrogen pump and water electrolysis demonstrations are carried out on interdigitated electrode (IDE) chips flexible with liquid supporting electrolytes and thin film polymer electrolytes. Notably, the mass activities of the nanostructured electrocatalysts from alkylated block copolymer templates are 35%–94% higher than electrocatalysts from non-alkylated block copolymer templates. Standing cylinder nanostructures lead to higher mass activities than lamellar variants despite their not having the largest surface area per unit catalyst loading demonstrating that mesostructure architectures have a profound impact on reactivity. Overall, IDE chips with model thin film electrocatalysts prepared from self-assembled block copolymers offer a high-throughput experimental method for correlating electrocatalyst nanostructure and composition to electrochemical reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electrochemical Reactivity and Passivation of Silicon Thin-Film Electrodes in Organic Carbonate Electrolytes

This work focuses on the mechanisms of interfacial processes at the surface of amorphous silicon thin-film electrodes in organic carbonate electrolytes to unveil the origins of the inherent nonpassivating behavior of silicon anodes in Li-ion batteries. Attenuated total reflection Fourier-transform infrared spectroscopy, X-ray absorption spectroscopy, and infrared near-field scanning optical microscopy were used to investigate the formation, evolution, and chemical composition of the surface layer formed on Si upon cycling. Herein, we found that the chemical composition and thickness of the solid/electrolyte interphase (SEI) layer continuously change during the charging/discharging cycles. This SEI layer “breathing” effect is directly related to the formation of lithium ethylene dicarbonate (LiEDC) and LiPF6 salt decomposition products during silicon lithiation and their subsequent disappearance upon delithiation. Furthermore, the detected appearance and disappearance of LiEDC and LiPF6 decomposition compounds in the SEI layer are directly linked with the observed interfacial instability and poor passivating behavior of the silicon anode.

25 ENERGY STORAGE↗
DOE OSTI2020

Optimization of Lithium Content and Sintering Additives in Tape Cast Lithium Garnet Electrolyte Sheets

The lithium garnet (LLZO) remains one of the most promising electrolyte materials for producing solid state batteries. Tape casting is one method for producing the thin ceramic electrolyte layer required for a high-performance solid state battery. Processing of LLZO is complicated by several factors including lithium volatilization, abnormal grain growth and phase instability. Many of these issues are exacerbated in tape cast sheets by the sheets' higher surface area to volume ratio, when compared to pellet processing methods. Here, we report on an environmentally friendly aqueous tape casting process for LLZO using methylcellulose as a binder and compare final sheet properties to other, solvent-based, options. Solids loading, binder content, dispersant composition, and wetting agent type are varied to improve ease of casting and enhance properties of the as-cast tape. Lithium content in sintered LLZO sheets is controlled by the inclusion of excess Li 2 CO 3 as lithium source in the ceramic tape itself and by a novel method of producing a lithium-saturated furnace atmosphere. Sintering time and temperature are optimized, and rapid thermal processing is investigated as a method of reducing lithium loss. Al 2 O 3 and MgO are examined for use as sintering additives. Characterization of LLZO sheets is performed with XRD, EIS and SEM. Li 2 CO 3 and sintering additive levels are optimized for ionic conductivity and density. The optimization effort improved the conductivity and density of 100µm thick sintered sheets to greater than 3x10 -4 S/cm conductivity and 90% density.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Preparing Li-garnet electrodes with engineered structures by phase inversion and high shear compaction processes

We report solid-state lithium batteries are promising for safety and energy density com-pared with traditional lithium-ion batteries. However, the large interfacial resistance between the electrode and electrolyte is a bottleneck to achieving high-performance solid-state batteries. Engineered electrode structures with a porous scaffold of the solid electrolyte material are promising to lower the interfacial resistance and provide a mechanical support for a thin solid electrolyte layer. In this work, two ceramic processing techniques are used to fabricate porous/dense bilayer architectures based on a Li 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZO) Li-garnet material. Finger-like vertically aligned pores are created by the phase inversion (PI) process. A water bath presaturated with Li salt prevents Li loss during the PI solvent exchange step. Pore size and porosity can be optimized by adjusting the bath temperature. The high shear compaction process was used to prepare LLZO tapes with 40, 60, and 80 vol% poreformer. The porosity of the tapes after sintering is 39.5%, 58.4%, and 75.4%, respectively. Microtomography exhibits the porosity, pore shape, and pore distribution of the tapes. A typical cathode material LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC) is filled into the pores via vacuum infiltration, and a dense cathode layer is formed within the garnet scaffold.

25 ENERGY STORAGE↗
DOE OSTI2020

Toward quantifying capacity losses due to solid electrolyte interphase evolution in silicon thin film batteries

To understand the origins of failure and limited cycle life in lithium-ion batteries (LIBs), it is imperative to quantitatively link capacity-fading mechanisms to electrochemical and chemical processes. This is extremely challenging in real systems where capacity is lost during each cycle to both active material loss and solid electrolyte interphase (SEI) evolution, two indistinguishable contributions in traditional electrochemical measurements. Here, we have used a model system in combination with (1) precision measurements of the overall Coulombic efficiency via electrochemical experiments and (2) x-ray reflectivity measurements of the active material losses. The model system consisted of a 515 Å thick amorphous silicon (a-Si) thin film on silicon carbide in half-cell geometry using a carbonate electrolyte with LiPF6 salt. This approach allowed us to quantify the capacity lost during each cycle due to SEI evolution. Combined with electrochemical analysis, we identify SEI growth as the major contribution to capacity fading. Specifically, the continued SEI growth results in increasing overpotentials due to increased SEI resistance, and this leads to lower extent of lithiation when the cutoff voltage is reached during lithiation. Our results suggest that SEI grows more with increased time spent at low voltages where electrolyte decomposition is favored. Finally, we extracted a proportionality constant for SEI growth following a parabolic growth law. Our methodology allows for the quantitative determination of lithium-ion loss mechanisms in LIBs by separately tracking lithium ions within the active materials and the SEI and offers a powerful method of quantitatively understanding LIB loss mechanisms.

25 ENERGY STORAGE↗
NASA NTRS2000

Electrolyte and Electrode Passivation for Thin Film Batteries

Passivation films for thin film batteries have been prepared and the conductivity and voltage stability window have been measured. Thin films of Li2CO3 have a large voltage stability window of 4.8V, which facilitates the use of this film as a passivation at both the lithium anode-electrolyte interface at high cathodic potentials.

passivation thin film batteries↗
NASA NTRS2002

Strength and Fracture Toughness of Solid Oxide Fuel Cell Electrolyte Material Improved

Solid oxide fuel cells (SOFC) are being developed for various applications in the automobile, power-generation, and aeronautics industries. Recently, the NASA Glenn Research Center has been exploring the possibility of using SOFC's for aeropropulsion under its Zero Carbon Dioxide Emission Technology (ZCET) Program. 10-mol% yttriastabilized zirconia (10YSZ) is a very good anionic conductor at high temperatures and is, therefore, used as an oxygen solid electrolyte in SOFC. However, it has a high thermal expansion coefficient, low thermal shock resistance, low fracture toughness, and poor mechanical strength. For aeronautic applications, the thin ceramic electrolyte membrane of the SOFC needs to be strong and tough. Therefore, we have been investigating the possibility of enhancing the strength and fracture toughness of the 10YSZ electrolyte without degrading its electrical conductivity to an appreciable extent. We recently demonstrated that the addition of alumina to zirconia electrolyte increases its strength as well as its fracture toughness. Zirconia-alumina composites containing 0 to 30 mol% of alumina were fabricated by hot pressing. The hot pressing procedure was developed and various hot pressing parameters were optimized, resulting in dense, crackfree panels of composite materials. Cubic zirconia and a-alumina were the only phases detected, indicating that there was no chemical reaction between the constituents during hot pressing at elevated temperatures. Flexure strength sf and fracture toughness K(sub IC) of the various zirconia-alumina composites were measured at room temperature as well as at 1000 C in air. Both properties showed systematic improvement with increased alumina addition at room temperature and at 1000 C. Use of these modified electrolytes with improved strength and fracture toughness should prolong the life and enhance the performance of SOFC in aeronautics and other applications.

Bansal, Narottam P.↗
DOE OSTI2024

Scalable Surface Micro-Texturing of LLZO Solid Electrolytes for Battery Applications

A challenge for lithium lanthanum zirconate (LLZO)-based solid-state batteries is to increase the critical current density (CCD) to enable high current cycling. A promising strategy is to modify the LLZO surface morphology to provide a larger contact area with the Li metal. Here, a surface-textured thin LLZO electrolyte was prepared through an easily scalable process. The texturing process is a simple pressing of green LLZO tapes between micro-textured substrates. A variety of textures can be produced, depending on the type of substrate, and texturing can be on either one side or both sides. For this work, after pressing and sintering, several micro-patterns are formed on thin LLZO (~118 μm thick). The properties of the various samples were characterized to investigate the impact of surface texturing, and the most promising ones were selected for electrochemical testing in symmetrical lithium cells and full cells. Li symmetric cells using a coarse ridge-textured LLZO exhibit ~2.5 times increased CCD compared to planar non-textured LLZO, and a solid-state full cell shows stable cycling and improved rate performance. Finally, we believe this process offers a favorable trade-off of processing complexity vs structural optimization to maximize CCD.

25 ENERGY STORAGE↗
DOE OSTI2020

Dendrite Growth Morphology Modeling in Liquid and Solid Electrolytes

The main goal of this project is to develop a multi-scale modeling approach that connects micron-scale phase-field models and atomic-scale density functional theory (DFT)-based simulations via parameter- and relationship-passing in order to predict Li-metal dendrite morphology evolution, in both liquid and solid electrolytes. The key hypothesis of the DFT-informed phase-field multiscale modeling approach is that it can capture the electrochemical-mechanical driving forces and incorporate the roles of nano-meter-thin solid electrolyte interphase (SEI) in liquid electrolytes as well as of the microstructures of micro-meter-thick solid electrolytes (SEs) for all-solid-state batteries. In this project, we have formulated and implemented phase-field models to incorporate the electrochemical driving forces in liquid electrolytes and then incorporate mechanical driving forces to simulate dendrite growth in solid electrolytes with resolved microstructures. We have implemented two treatments for the SEI: an explicit model to include the microstructure of the SE or SEI in the phase field model and an implicit model to simulate the impact of nano-meter thick SEI in liquid electrolytes by varying the electrode/electrolyte interfacial properties. The key interfacial properties, including the electronic and ionic transport properties, the charge transfer reaction kinetics, and mechanical properties, were computed by DFT-based calculations. At the DFT-based model, one key advancement is to directly predict the charge transfer reaction kinetics at a complex Li/SEI/electrolyte interface by linking DFT with density functional tight binding (DFTB) calculations. As the main accomplishments, we have demonstrated two successful predictions in both solid electrolyte and liquid electrolyte based on this multiscale approach. The predicted intergranular Li dendrite growth in LLZO revealed the importance of trapped electrons at internal interfaces in the microstructure of LLZO. The predicted electroplating morphology of mossy Li and faceted Mg agreed well with experiments. The insights provided by the multiscale model and the model enabled electrolyte and SEI design will accelerate the development of Li-metal electrode for high energy density batteries, that meet DOE’s target on cell density (>350 Wh/kg) and cost below $100/kWhuse for EV applications.

25 ENERGY STORAGE↗
DOE OSTI2025

Rapid scalable plasma processing of thin-film Li–La–Zr–O solid-state electrolytes

Solid-state electrolytes, such as lithium lanthanum zirconium oxide (LLZO), show promise as technologies for next-generation high-energy-density batteries, but commercial development has been hindered by a lack of scalable processing methods. Current fabrication methods are costly or require long annealing steps to create dense films. We report an atmospheric pressure blown-arc nitrogen plasma jet process to rapidly form sub-micrometer-thick, dense amorphous LLZO (a-LLZO) films from sol-gel precursors. Films are processed in less than 2 min, an order of magnitude faster than what has previously been reported. We demonstrate 500-nm-thick a-LLZO films processed at 350°C with an ionic conductivity of 2 × 10 −6 S/cm at 30°C and 2 × 10 −3 S/cm at 100°C and a conductance of 19 S at 100°C, the highest conductance of any LLZO phase to date. Here, the films exhibit outstanding smooth surface morphology with low defectivity, advancing atmospheric plasma processing as a scalable processing method for solid-state electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2022

Sulfide glass solid-state electrolyte separators for Li metal batteries: using an interlayer to increase rate performance and reduce stack pressure

We report on the solubility of (Li 2 S) 60 (SiS 2 ) x (P 2 S 5 ) 40–x , (0 ≤ x ≤ 40) sulfide glass solid-state electrolytes in the 1:1 (v/v) DME:DOL solvent mixture, a popular choice for lithium metal battery liquid electrolytes. SiS 2 -rich glasses within the compositional range of (Li 2 S) 60 (SiS 2 ) x (P 2 S 5 ) 40–x (28 ≤ x ≤ 40) were found to be functionally insoluble in DME:DOL. Hybrid symmetric test cells with a thin liquid electrolyte layer (0.6 M LiTFSI + 0.4 M LiNO 3 in 1:1 (v/v) DME:DOL) at the interface between lithium metal electrodes and an insoluble (Li 2 S) 60 (SiS 2 ) 28 (P 2 S 5 ) 12 glass wafer were tested. Hybrid test cells delivered a critical current density of 3.0 mA cm –2 at 25 °C and 0.1 MPa, which is nearly double the CCD of comparable dry symmetric test cells cycled at 10× higher stack pressure.

25 ENERGY STORAGE↗
DOE OSTI2020

Boosting solid oxide fuel cell performance via electrolyte thickness reduction and cathode infiltration

Increasing the power density and reducing the operating temperature of solid oxide fuel cells (SOFCs) is important for improving commercial viability. Here we discuss two strategies for achieving such improvements in Ni–YSZ supported SOFCs – electrolyte thickness reduction and cathode infiltration. Microstructural and electrochemical results are presented showing the effect of reducing YSZ/GDC electrolyte thickness from 8 to 2.5 μm, and the effect of PrO x infiltration into the LSCF–GDC cathode. Both of these measures are effective, particularly at lower temperatures, leading to an increase in the maximum power density at 650 °C from 0.4 to 0.95 W cm –2 , for example. Electrochemical impedance spectroscopy utilizing subtractive analysis shows that PrO x enhances the cathode charge transfer process. Reducing the electrolyte thickness reduces not only the cell ohmic resistance but also the electrode polarization resistance. Furthermore, the latter effect appears to be an artifact associated with a slight increase in the steam partial pressure at the anode due to minor gas leakage across the thinner electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2022

Physical and Mechano-Electrochemical Phenomena of Thin Film Lithium-Ceramic Electrolyte Constructs

While a small number of solid electrolytes exhibit high ionic conductivity (~1mS cm at 298K), few are stable against Li metal. The garnet-type solid electrolyte, based on the nominal formula Li 7 La 3 Zr 2 O 12 (LLZO), is unique in that it is a fast ion conductor and – as we demonstrated in our recent project (DE-EE-00006821) – is stable against Li. Moreover, our former project successfully demonstrated a decrease in Li-LLZO interface resistance from 12,000 to 2 Ohms cm 2 and stable cycling at 1 mA cm 2 for 100 cycles (+/- 15 µm Li per cycle). Although the past project (DE-EE-00006821) demonstrated LLZO is a viable solid electrolyte for enabling batteries using metallic Li, the studies used thick pellets (1mm) and thick anodes (~500 µm). We believe that to achieve a step increase in technology readiness level (TRL), the same performance characteristics previously shown should be demonstrated in technologically relevant cells, e.g. thin LLZO and thin Li. The goal of this project is to acquire a deep fundamental understanding of the physical and mechano-electrochemical phenomena that control the performance of cells consisting of thin LLZO (~10 µm), thin Li anodes (~20 µm) and thin solid-state composite cathodes. If successful, the knowledge gained in this project will guide closely related commercialization efforts to scale the production of LLZO-based solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Characteristics of Oxygen Electrode Supported Reversible Solid Oxide Cells

Oxygen-electrode-supported solid oxide cells (OESCs) have potential advantages over fuel-electrode-supported cells, including reduced fuel-electrode concentration polarization, better oxygen electrode current collection, and flexibility in the fuel electrode choice. However, there are serious drawbacks including the difficulty of co- firing the oxygen electrode and electrolyte, and oxygen electrode concentration polarization. This paper explores the characteristics of OESCs with La 0.8 Sr 0.2 MnO 3-δ -Zr 0.92 Y 0.16 O 2-δ (LSM-YSZ) electrode-support enhanced by SrTi 0.3 Fe 0.6 Co 0.1 O 3-δ (STFC) infiltration, thin YSZ electrolyte, and SrTi 0.3 Fe 0.7 O 3-δ (STF) fuel electrodes. Here, the STFC infiltration increases fuel cell maximum power density by > 1.5 times and electrolysis current density (at 1.3 V) by > 2 times. Cell performance in pure oxygen is compared to that in air, exploring a possible reversible solid oxide cell system configuration where oxygen produced during electrolysis is stored and subsequently used during fuel cell operation. The fuel cell maximum power density is increased from 0.88 W cm -2 in air to 1.37 W cm -2 in oxygen, with limiting current increased from 1.7 to >5.6 A cm -2 ; the electrolysis performance is essentially unchanged, probably because the electrode air becomes enriched with oxygen during electrolysis.

25 ENERGY STORAGE↗